Explosive complexes

ABSTRACT

Lead-free primary explosives of the formula [M II (A) R (B X ) S ](C Y ) T , where A is 1,5-diaminotetrazole, and syntheses thereof are described. Substantially stoichiometric equivalents of the reactants lead to high yields of pure compositions thereby avoiding dangerous purification steps.

CROSS REFERENCE TO RELATED APPLICATION

The following is a divisional application of U.S. patent applicationSer. No. 11/707,610, filed Feb. 15, 2007.

STATEMENT OF FEDERAL RIGHTS

The United States government has rights in this invention pursuant toContract No. DE-AC52-06NA25396 between the United States Department ofEnergy and Los Alamos National Security, LLC for the operation of LosAlamos National Laboratory.

FIELD OF INVENTION

The present invention relates to lead-free primary explosives.

BACKGROUND

Explosives are categorized as primary or secondary based on theirsusceptibility to initiation. Primary explosives are highly susceptibleto initiation and are used in small quantities to ignite secondaryexplosives, main charges, propellants, or fuel. Requirements for primaryexplosives include sufficient sensitivity to be detonated reliably whilenot being exceedingly dangerous to handle as well as sufficient thermalstability to not decompose on extended storage or thermal insult.

Two common primary explosives are lead azide and lead styphnate, butboth emit toxic lead upon detonation. Because of this toxic residue, thedevelopment of a lead-free primary explosive is needed.

SUMMARY OF INVENTION

The present invention discloses novel lead-free compounds and synthesesthereof. More particularly, the present invention is directed tocompounds of the formula [M^(II)(A)_(R)(B^(X))_(S)](C^(Y))_(T) andsyntheses thereof, wherein

M is selected from the group consisting of

-   -   (1) cobalt,    -   (2) copper,    -   (3) iron,    -   (4) manganese,    -   (5) nickel, and    -   (6) zinc;

A is 1,5-diaminotetrazole (“DAT”);

B is selected from the group consisting of

-   -   (1) water (“H₂O”)    -   (2) 5-aminotetrazole (“AT”),    -   (3) 5-aminotetrazolate (“AT⁻”),    -   (4) 5-nitrotetrazolate (“NT⁻”),    -   (5) 3,5-dinitro-1,2,4-triazolate (“DNT⁻”),    -   (6) 5-azido-3-nitro-1,2,4-triazolate (“ANT⁻”),    -   (7) azide (“N₃ ⁻”), and    -   (8) nitrate (“NO₃ ⁻”);

C is selected from the group consisting of

-   -   (1) AT⁻,    -   (2) ANT⁻,    -   (3) DNT⁻,    -   (4) NO₃ ⁻,    -   (5) N₃ ⁻,    -   (6) NT⁻,    -   (7) perchlorate (“ClO₄ ⁻”),    -   (8) tetraazidoborate (“TAB⁻”),    -   (9) dinitramide (“DN⁻”),    -   (10) nitroformate (“NF⁻”),    -   (11) 5,5′-diazido-2,2′-azo-1,3,4-triazolate (“DAAT²⁻”),    -   (12) 5,5′-dinitro-2,2′-azo-1,3,4-triazolate (“DNAT²⁻”),    -   (13) 4,4′,5,5′-tetranitro-2,2′-biimidazolate (“TNBl²⁻”), and    -   (14) 5,5′-azotetrazolate (“AZT²⁻”),    -   R is 5 or 6;    -   S is 0 or 1;    -   T is 1 or 2;    -   X is 0 or −1;    -   Y is −1 or −2;    -   X+Y=−2; and    -   R+S=6.

The above compound can be prepared according to the reaction[M^(II)(H₂O)₆]D₂+R(A)+S(B^(X))+T(C^(Y))→[M^(II)(A)_(R)(B^(X))_(S)]C^(Y))_(T)wherein

M is selected from the group consisting of

-   -   (1) cobalt,    -   (2) copper,    -   (3) iron,    -   (4) manganese,    -   (5) nickel, and    -   (6) zinc;

A is DAT;

B is selected from the group consisting of

-   -   (1) H₂O,    -   (2) AT,    -   (3) AT⁻,    -   (4) NT⁻,    -   (5) DNT⁻,    -   (6) ANT⁻,    -   (7) N₃ ⁻, and    -   (8) NO₃ ⁻;

C is selected from the group consisting of

-   -   (1) AT⁻,    -   (2) ANT⁻,    -   (3) DNT⁻,    -   (4) NO₃ ⁻,    -   (5) N₃ ⁻,    -   (6) NT⁻,    -   (7) ClO₄ ⁻,    -   (8) TAB⁻,    -   (9) DN⁻,    -   (10) NF⁻,    -   (11) DAAT²⁻,    -   (12) DNAT²⁻,    -   (13) TNBl²⁻, and    -   (14) AZT²⁻;

D is selected from the group consisting of

-   -   (1) CO₄ ⁻,    -   (2) NO₃ ⁻, and    -   (3) Cl⁻;

R is 5 or 6;

S is 0 or 1;

T is 1 or 2;

X is 0 or −1;

Y is −1 or −2;

X+Y=−2; and

R+S=6 as follows:

(1) mixing a chosen quantity of a metal salt [M^(II)(H₂O)₆]D₂ and Rmolar equivalents of A in a suitable solvent, thereby forming a firstsolution;

(2) heating said first solution at a time and temperature suitable forthe color of said first solution to change;

(3) adding S molar equivalents of B^(X) to said first solution, therebyforming a second solution;

(4) heating said second solution at a time and temperature suitable forgenerating a third solution containing a cationic complex;

(5) adding T molar equivalents of C^(Y) to said third solutioncontaining said cationic complex at a time and temperature suitable toform said compound;

(6) cooling said third solution to room temperature; and

(7) separating said compound from said third solution.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: (A) shows a copper embodiment of the lead-free compound[Cu^(II)(DAT)₅(H₂O)](ClO₄)₂. (B) shows a copper embodiment of thelead-free compound [Cu^(II)(DAT)₅(NO₃)]NO₃. (C) shows an iron embodimentof the lead-free compound [Fe^(II)(DAT)₆](ClO₄)₂. (D) shows a copperembodiment of the lead-free compound [Cu^(II)(DAT)₆](ClO₄)₂.

FIG. 2: (A) and (B) show two scanning electron microscope outputs forthe copper embodiment of the lead-free compound[Cu^(II)(DAT)₅(H₂O)](ClO₄)₂. (A) has a magnification of 1,000. (B) has amagnification of 10,000. (C) and (D) show two scanning electronmicroscope outputs for the iron embodiment of the lead-free compound[Fe^(II)(DAT)₆](ClO₄)₂. (C) has a magnification of 1,000. (D) has amagnification of 10,000. (E) and (F) show two scanning electronmicroscope outputs for the copper embodiment of the lead-free compound[Cu^(II)(DAT)₆](ClO₄)₂. (E) has a magnification of 1,000. (F) has amagnification of 10,000.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to compounds of the formula[M^(II)(A)_(R)(B^(X))_(S)](C^(Y))_(T) and syntheses thereof, wherein

M is selected from the group consisting of

-   -   (1) cobalt,    -   (2) copper,    -   (3) iron,    -   (4) manganese,    -   (5) nickel, and    -   (6) zinc;

A is DAT;

B is selected from the group consisting of

-   -   (1) H₂O,    -   (2) AT,    -   (3) AT⁻,    -   (4) NT⁻,    -   (5) DNT⁻,    -   (6) ANT⁻,    -   (7) N₃ ⁻, and    -   (8) NO₃ ⁻;

C is selected from the group consisting of

-   -   (1) AT⁻,    -   (2) ANT⁻,    -   (3) DNT⁻,    -   (4) NO₃ ⁻,    -   (5) N₃ ⁻,    -   (6) NT⁻,    -   (7) ClO₄ ⁻,    -   (8) TAB⁻,    -   (9) DN⁻,    -   (10) NF⁻,    -   (11) DAAT²⁻,    -   (12) DNAT²⁻,    -   (13) TNBl²⁻, and    -   (14) AZT²⁻;

R is 5 or 6;

S is 0 or 1;

T is 1 or 2;

X is 0 or −1;

Y is −1 or −2;

X+Y=−2; and

R+S=6.

The above compound can be prepared according to the reaction[M^(II)(H₂O)₆]D₂+R(A)+S(B^(X))+T(C^(Y))→[M^(II)(A)_(R)(B^(X))_(S)](C^(Y))_(T)wherein

M is selected from the group consisting of

-   -   (1) cobalt,    -   (2) copper,    -   (3) iron,    -   (4) manganese,    -   (5) nickel, and    -   (6) zinc;

A is DAT;

B is selected from the group consisting of

-   -   (1) H₂O,    -   (2) AT,    -   (3) AT⁻,    -   (4) NT⁻,    -   (5) DNT⁻,    -   (6) ANT⁻,    -   (7) N₃ ⁻, and    -   (8) NO₃ ⁻;

C is selected from the group consisting of

-   -   (1) AT⁻,    -   (2) ANT⁻,    -   (3) DNT⁻,    -   (4) NO₃ ⁻,    -   (5) N₃ ⁻,    -   (6) NT⁻,    -   (7) ClO₄ ⁻,    -   (8) TAB⁻,    -   (9) DN⁻,    -   (10) NF⁻,    -   (11) DAAT²⁻,    -   (12) DNAT²⁻,    -   (13) TNBl²⁻, and    -   (14) AZT²⁻;

D is selected from the group consisting of

-   -   (1) ClO₄ ⁻,    -   (2) NO₃ ⁻, and    -   (3) Cl⁻;

R is 5 or 6;

S is 0 or 1;

T is 1 or 2;

X is 0 or −1;

Y is −1 or −2;

X+Y=−2; and

R+S=6 as follows:

(1) mixing a chosen quantity of a metal salt [M^(II)(H₂O)₆]D₂ and Rmolar equivalents of A in a suitable solvent, thereby forming a firstsolution:

(2) heating said first solution at a time and temperature suitable forthe color of said first solution to change;

(3) adding S molar equivalents of B^(X) to said first solution, therebyforming a second solution;

(4) heating said second solution at a time and temperature suitable forgenerating a third solution containing a cationic complex;

(5) adding T molar equivalents of C^(Y) to said third solutioncontaining said cationic complex at a time and temperature suitable toform said compound;

(6) cooling said third solution to room temperature; and

(7) separating said compound from said third solution.

In step 1, a suitable solvent is an ethanolic solvent or an acidicethanolic solvent (a mixture of absolute ethanol and two drops of acidwith a pH measurement ranging from about 0 to about 2). In step 4, thesecond solution can be heated anywhere from about above room temperatureto reflux and for a time in the range of from about 30 minutes to 3hours or until the solution becomes colorless. In step 6, the thirdsolution is preferably slowly cooled to 40° C. with gentle stirring, andthen the third solution is allowed to cool to room temperatureundisturbed. Gentle stirring can achieve small particle sizes forsubsequent safe handling. Depending on the nature of C^(Y), theethanolic reaction solution may be reduced in volume, or the temperatureis lowered using an ice-bath to precipitate the compound.

Dangerous purification steps can be avoided by employing an absoluteethanolic solvent and stoichiometric equivalents of the reactants toform a nearly quantitative single product. An acidic solvent or excessquantity of any reactant might result in impurities.

Reference is now made in detail to four embodiments of the invention.These four embodiments are [Cu^(II)(DAT)₅(H₂O](ClO₂)₂,[Cu^(II)(DAT)₅(NO₃)]NO₃, [Fe^(II)(DAT)₆](ClO₄)₂, and[Cu^(II)(DAT)₆](ClO₄)₂ which may have the configurations shown in FIGS.1A-1D.

The embodiment of [Cu^(II)(DAT)₅(H₂O)](ClO₄)₂ can be prepared byrefluxing a solution of copper salt having the formula[Cu^(II)(H₂O)₆](ClO₄)₂ and 5 molar equivalents of DAT in a suitablesolvent. The resulting precipitate is filtered and washed thoroughlywith fresh, cold ethanol. The reaction gives nearly quantitative yieldand an analytically pure product of [Cu^(II)(DAT)₅(H₂O)](ClO₄)₂ withoutadditional recrystallization or purification.

The embodiment of [Cu^(II)(DAT)₅(NO₃)]NO₃ can be prepared by refluxing asolution of a copper salt having the formula [Cu^(II)(H₂O)₆](NO₃)₂ and 5molar equivalents of DAT in a suitable solvent. The resultingprecipitate is filtered and washed thoroughly with fresh, cold ethanol.The reaction gives nearly quantitative yield and an analytically pureproduct of [Cu^(II)(DAT)₆(NO₃)](—NO₃—) without additionalrecrystallization or purification.

The embodiment of [Fe^(II)(DAT)₆](ClO₄)₂ can be prepared by refluxing asolution of an iron salt having the formula [Fe^(II)(H₂O)₆](ClO₄)₂ and 6molar equivalents of DAT in a suitable solvent. The resultingprecipitate is filtered and washed thoroughly with fresh, cold ethanol.The reaction gives nearly quantitative yield and an analytically pureproduct of [Fe^(II)(DAT)₆](ClO₄)₂ without additional recrystallizationor purification.

The embodiment of [Cu^(II)(DAT)₆](ClO₄)₂ can be prepared by refluxing asolution of a copper salt having the formula [Cu^(II)(H₂O)₆](ClO₄)₂ and6 molar equivalents of DAT in a suitable solvent. The resultingprecipitate is filtered and washed thoroughly with fresh, cold ethanol.The reaction gives nearly quantitative yield and an analytically pureproduct of [Cu^(II)(DAT)₆](ClO₄)₂ without additional recrystallizationor purification.

EXAMPLE 1 Preparation of [Cu^(II)(DAT)₅(H₂O](ClO₄)₂

A copper compound was prepared in accordance with the reaction[Cu^(II)(H₂O)₆](ClO₄)₂+5DAT→[Cu^(II)(DAT)₅(H₂O)](ClO₄)₂ as follows:

-   -   (a) 0.15 grams (“g”) of cupric perchlorate was completely        dissolved in 40 milliliters (“mL”) of absolute ethanol;    -   (b) 0.203 g of DAT was slowly added to the solution of cupric        perchlorate;    -   (c) the resulting solution was heated to reflux for between 2        hours and 3 hours or until the mother liquor was completely        clear and colorless;    -   (d) the solution was cooled to about 40° C. with slow stirring        and then allowed to cool to room temperature undisturbed;    -   (e) the precipitate was filtered out of the mother liquor,        thereby accumulating a collected solid;    -   (f) the collected solid was washed thoroughly with fresh, cold,        absolute ethanol;    -   (g) the undried collected solid was wet transferred into a        Teflon-vial using a plastic spatula with care taken to avoid        scraping or friction between the spatula and walls of the vial;        and    -   (h) the collected solid was air-dried prior to use.

Elemental analysis of the collected solid, as set forth in TABLE 1showed the composition corresponds to [Cu^(II)(DAT)₅(H₂O)](ClO)₂.

TABLE 1 CARBON (%) HYDROGEN (%) NITROGEN (%) THEORETICAL 7.69 2.84 53.81OBSERVED 7.54 ± 0.4 2.57 ± 0.4 51.18 ± 0.4

The above-described synthesis yielded about 91%[Cu^(II)(DAT)₅(H₂O)](ClO₄)₂.

FIG. 2A shows two scanning electron microscope outputs for the copperembodiment of the lead-free compound [Cu^(II)(DAT)₅(H₂O)](ClO₄)₂.

The left output has a magnification of 1,000. The right output has amagnification of 10,000.

The density of the copper compound was 1.98 grams per cubic centimeter(“g/cm³”) using a liquid pycnometry technique. The thermal decompositiontemperature was 224° C. (on a 5-7 microgram (“μg”) sample) as determinedby Differential Scanning calorimetry (“DSC”).

Explosive initiation data of the dry collected solid were as follows:

-   Friction: 15 g determined on a 1-1.5 milligram (“mg”) sample using    mini BAM;-   Impact: 5 cm on a 5 mg sample determined by a type 12 impact    machine;-   Spark: 0.06875 joules (“J”) determined by ABL Electrostatic    Discharge.

EXAMPLE 2 Preparation of [Cu^(II)(DAT)₅(NO₃)]NO₃

A copper compound was prepared in accordance with the reaction[Cu^(II)(H₂O)₆](NO₃)₂+5DAT→[Cu^(II)(DAT)₅(NO₃)]NO₃ as follows:

-   -   (a) 0.30 g of cupric nitrate was completely dissolved in 40 mL        of absolute ethanol;    -   (b) 0.405 g of DAT was slowly added to the solution of cupric        nitrate;    -   (c) the resulting solution was heated to reflux for between 2        hours and 3 hours or until the mother liquor was completely        clear and colorless;    -   (d) the solution was cooled to about 40° C. with slow stirring        and then allowed to cool to room temperature undisturbed;    -   (e) the precipitate was filtered out of the mother liquor,        thereby accumulating a collected solid;    -   (f) the collected solid was washed thoroughly with fresh, cold,        absolute ethanol;    -   (g) the undried collected solid was wet transferred into a        Teflon-vial using a plastic spatula with care taken to avoid        scraping or friction between the spatula and walls of the vial;        and    -   (h) the collected solid was air-dried prior to use.

Elemental analysis of the collected solid, as set forth in TABLE 2,showed the composition corresponds to [Cu^(II)(DAT)₅(NO₃)]NO₃.

TABLE 2 CARBON (%) HYDROGEN (%) NITROGEN (%) THEORETICAL 8.73 2.93 65.15OBSERVED 8.77 ± 0.4 2.82 ± 0.4 63.23 ± 0.4

The above-described synthesis yielded about 94% [Cu^(II)(DAT)₅(NO₃)]NO₃.

The density of the copper compound was 2.08 g/cm³ using a liquidpycnometry technique. The thermal decomposition temperature was 228° C.(on a 7-8 μg sample) as determined by DSC.

Explosive initiation data of the dry collected solid were as follows:

-   Friction: 2.0 kg determined on a 1-1.5 mg sample using BAM;-   Impact: 10 cm on a 5 mg sample determined by a type 12 impact    machine;-   Spark: 3.125 J determined by ABL Electrostatic Discharge.

EXAMPLE 3 Preparation of [Fe^(II)(DAT)₆](ClO₄)₂

An iron compound was prepared in accordance with the reaction[Fe^(II)(H₂O)₆](ClO₄)₂+6 DAT→[Fe^(II)(DAT)₆](ClO₄)₂ as follows:

-   -   (a) 0.20 g of ferrous perchlorate was completely dissolved in 40        mL of absolute ethanol:    -   (b) 0.331 g of DAT was slowly added to the solution of ferrous        perchlorate;    -   (c) the resulting solution was heated to reflux for between 2        hours and 3 hours or until the mother liquor was completely        clear and colorless;    -   (d) the solution was cooled to about 40° C. with slow stirring        and then allowed to cool to room temperature undisturbed;    -   (e) the precipitate was filtered out of the mother liquor,        thereby accumulating a collected solid;    -   (f) the collected solid was washed thoroughly with fresh, cold,        absolute ethanol;    -   (g) the undried collected solid was wet transferred into a        Teflon-vial using a plastic spatula with care taken to avoid        scraping or friction between the spatula and walls of the vial;        and    -   (h) the collected solid was air-dried prior to use.

Elemental analysis of the collected solid, as set forth in TABLE 3,showed the composition corresponds to [Fe^(II)(DAT)₆](ClO₄)₂.

TABLE 3 CARBON (%) HYDROGEN (%) NITROGEN (%) THEORETICAL 8.43 2.83 58.96OBSERVED 8.60 ± 0.4 2.92 ± 0.4 58.23 ± 0.4

The above-described synthesis yielded about 93% [Fe^(II)(DAT)₆](ClO₄)₂.

FIG. 2B shows two scanning electron microscope outputs for the ironembodiment of the lead-free compound having a formula[Fe^(II)(DAT)₆](ClO₄)₂. The left output has a magnification of 1,000.The right output has a magnification of 10,000.

The density of the iron compound was 2.03 g/cm³ using a liquidpycnometry technique. The thermal decomposition temperature was 194° C.(on a 4-5 μg sample) as determined by DSC.

Explosive initiation data of the dry collected solid were as follows:

-   Friction: <10 g determined on a 1-1.5 mg sample using mini BAM;-   Impact: 5 cm on a 5 mg sample determined by a type 12 impact    machine;-   Spark: 0.0375 J determined by ABL Electrostatic Discharge.

EXAMPLE 4 Preparation of [Cu^(II)(DAT)₆](ClO₄)₂

A copper compound was prepared in accordance with the reaction[Cu^(II)(H₂O)₆](ClO₄)₂+6 DAT→[Cu^(II)(DAT)₆](ClO₄)₂ in a manner similarto that described in EXAMPLE 1 for the preparation of[Cu^(II)(DAT)₅(H₂O)](ClO₄)₂ herein above, except that 6 molarequivalents of DAT are used in step (b).

Elemental analysis of the collected solid, as set forth in TABLE 4,showed the composition corresponds to [Cu^(II)(DAT)₆](ClO₄)₂.

TABLE 4 CARBON (%) HYDROGEN (%) NITROGEN (%) THEORETICAL 8.35 2.80 58.43OBSERVED 7.97 ± 0.4 2.64 ± 0.4 54.43 ± 0.4

The above-described synthesis yielded about 94% [Cu^(II)(DAT)₆](ClO₄)₂.

FIG. 2C shows two scanning electron microscope outputs for a copperembodiment of the lead-free compound having a formula[Cu^(II)(DAT)₆](ClO₄)₂. The left output has a magnification of 1,000.The right output has a magnification of 10,000.

The density of the copper compound was 2.14 g/cm³ using a liquidpycnornetry technique. The thermal decomposition temperature was 232° C.(on a 4-5 μg) as determined by DSC.

Explosive initiation data of the dry collected solid were as follows:

-   Friction: <10 g determined on a 1-1.5 mg sample using mini BAM;-   Impact: 5 cm on a 5 mg sample determined by a type 12 impact    machine;-   Spark: 0.03125 J determined by ABL Electrostatic Discharge.

It is understood that the foregoing detailed description and examplesare merely illustrative and are not to be taken as limitations upon thescope of the invention, which is defined by the appended claims. Variouschanges and modifications to the disclosed embodiments will be apparentto those skilled in the art. Such changes and modifications, includingwithout limitation those relating to chemical structures, syntheses,formulations and/or methods of use of the invention, may be made withoutdeparting from the spirit and scope thereof.

1. A process for preparing a compound according to the reaction[M^(II)(H₂O)₆]D₂+R(A)→[M^(II)(A)_(R)(H₂O)_(6-R)(D)_(X)](D)_(2-X) M isselected from the group consisting of (1) cobalt, (2) copper, (3) iron,(4) manganese, (5) nickel, and (6) zinc; A is DAT; D is selected fromthe group consisting of (1) ClO₄ ⁻, (2) NO₃ ⁻, and (3) Cl⁻; R is 5 or 6;and X is 0 or 1; and R+X=6 as follows: (1) mixing a chosen quantity of ametal salt [M^(II)(H₂O)₆]D₂ and R molar equivalents of A in a suitablesolvent, thereby forming a solution; (2) heating said solution at a timeand temperature suitable for the color of said solution to change; (3)cooling said solution to room temperature to form a precipitate of thecompound; and (4) filtering the precipitate of the compound.
 2. Theprocess of claim 1 wherein R is
 6. 3. The process of claim 1 wherein Mis iron.
 4. The process of claim 1 wherein R is
 5. 5. The process ofclaim 1 wherein said suitable solvent is an ethanolic solvent.
 6. Theprocess of claim 1 wherein said solution is heated in stop step 2 toreflux for between 2 to 3 hours or until clear and colorless.
 7. Theprocess of claim 1 wherein said solution is cooled in step 2 to around40° C. with gentle stirring and then cooled to room temperatureundisturbed.